Flow systems exploiting in-line prior assays

An expert sequential injection system involving a prior assay is proposed for spectrophotometric determination of phosphate and eventually zinc in soil extracts. The result of phosphate determination is the basis for a concentration-oriented decision regarding to the need or not for zinc determination. Zinc was only determined if a threshold value (peak height corresponding to 5.0 mg l⁻¹ P) was surpassed. The methods involved formation of molybdenum blue and the Rhodamine 6G/ammonium thiocyanate/Zn²⁺ ternary complex. Variations in the threshold value were < 2% during 4 h operating periods, false responses were not verified, and the analytical time was reduced in about 30%. Precise results (R.S.D. <3% P and < 1% Zn) in agreement with spectrophotometry and flame atomic absorption spectrometry were obtained. The innovation permits faster information processing, as well as a reduction in the number of measurements, number of analytical steps, laboratorial time, and consumption of sample and reagents, thus waste generation.     

Gas chromatography/mass spectrometric study of non-commercial C-4-substituted 1,4-dihydropyridines and their oxidized derivatives

A gas chromatography/mass spectrometry (GC/MS) method for the qualitative and quantitative determination of the calcium-channel antagonists C-4-substituted 1,4-dihydropyridines, and their corresponding N-ethyl derivatives, is presented. Also, the electrochemical oxidation and the reactivity of the compounds with alkyl radicals derived from 2,2'-azobis-(2-amidinopropane) were monitored by GC/MS. Mass spectral fragmentation patterns for the C-4-substituted 1,4-dihydropy-ridine parent drugs were significantly different from those of their oxidation products, generated either by electrochemical oxidation or by reaction with alkyl radicals. However, for N-ethyl-1,4-dihydropyridine compounds it was not possible to detect the final products (pyridinium salts) using these experimental conditions.     

Spectrophotometric flow-injection determination of zinc in plant digests based on a spot test

A spot test was implemented in a flow-injection system for the spectrophotometric determination of zinc in digests of plant materials. It is based on the influence of Zn²⁺ on the oxidation rate of 1-naphthylethylenediamine (NED) by hexacyanoferrate(III) under acidic conditions. In order to control the precipitate formation and to maintain the resulting suspension, a micellar medium was established by adding Triton X-100. The proposed system handles about 65 samples per hour, meaning 72 μg NED and 9.0 mg K₃[Fe(CN)₆] per determination. Baseline drift is usually <0.01 absorbance per hour and the analytical signals for 0.5-2.5 mg l⁻¹ Zn range within ca. 0.07-0.45 absorbance. Linearity of the analytical curve is fair (r>0.999, n=6) and detection limit was estimated as 0.2 mg l⁻¹ Zn. Results are precise (R.S.D.<1%, n=10) and in agreement with flame atomic absorption spectrometry and with certified values of standard reference materials.     

Amorphous Calcium Phosphates: Solvent-Controlled Growth and Stabilization through the Epoxide Route

Calcium phosphates stand among the most promising nanobiomaterials in key biomedical applications, such as bone repairment, signalling or drug/gene delivery. Their intrinsic properties as crystalline structure, composition, particle shape and size define their successful use. Among these compounds, metastable amorphous calcium phosphate (ACP) is currently gaining particular attention due to its inherently high reactivity in solution, which is crucial in bone development mechanisms. However, the preparation of this highly desired (bio)material with control over its shape, size and phase purity remains as a synthetic challenge. In this work, the epoxide route was adapted for the synthesis of pure and stable ACP colloids. By using biocompatible solvents, such as ethylene glycol and/or glycerine, it was possible to avoid the natural tendency of ACP to maturate into more stable and crystalline apatites. Moreover, this procedure offers size control, ranging from small nanoparticles (60 nm) to micrometric spheroids (>500 nm). The eventual fractalization of the internal mesostructured can be tuned, by simply adjusting the composition of the ethylene glycol:glycerine solvent mixture. These findings introduce the use of green solvents as a new tool to control crystallinity and/or particle size in the synthesis of nanomaterials, avoiding the use of capping agents and preserving the natural chemical reactivity of the pristine surface.     

High-sensitivity methods for sequential injection determination of the main constituents of alloys

A sequential injection system with spectrophotometric detection was proposed for the determination of copper, zinc and lead in brass. In view of the high analyte concentrations and the sensitivity of the involved catalytic methods, optimization of the flow system was carried out aiming mild reaction conditions. Copper and lead determinations were based on the catalytic effects of Cu²⁺ and Pb²⁺ on the oxidation rates of resorcinol and pyrogallol red by H₂O₂, respectively, and zinc determination involved precipitate formation after oxidation of 1-nafthylethylenediamine by K₃Fe(CN)₆. The analytical procedures were designed with some common parameters such as pH=9.0 (borate system), λ=530 nm, and H₂O₂ as oxidizing agent; system geometry was maintained.The proposed system is rugged, and base line drift is not observed during 4 h operation periods. Twenty samples are run per hour (60 determinations) and reagent consumption is minimal, thus avoiding drawbacks related to waste management. Precise results (R.S.D.<1.0%; n=7) are obtained and a detection limit of 1% (w/w) was estimated for the three analytes. Results were in agreement with flame atomic absorption spectrometry.     

A column generation approach for location-routing problems with pickup and delivery

In this paper we formulate an integer programming model for the Location and Routing Problem with Pickup and Delivery. We propose a column generation scheme and implement, for the subproblem, a label-setting algorithm for the shortest path with pickup and delivery and time windows problem. We also propose a set of heuristics to speed up this process. To validate the model, we implement the column generation scheme and test it on different instances developed in this paper. We also provide an analysis of how the costs of opening depots and the fixed cost of routes affect the optimal solution.     

Stealth scalar field overflying a 2+1 black hole

A nontrivial scalar field configuration of vanishing energy-momentum is reported. These matter configurations have no influence on the metric and therefore they are not be “detected" gravitationally. This phenomenon occurs for a time–dependent nonminimally coupled and self-interacting scalar field on the 2+1 (BTZ) black hole geometry. We conclude that such stealth configurations exist for the static 2+1 black hole for any value of the nonminimal coupling parameter ζ≠0 with a fixed self-interaction potential U _ζ(Φ). For the range 0 < ζ≤1/2 potentials are bounded from below and for the range 0 < ζ < 1/4 the stealth field falls into the black hole and is swallowed by it at an exponential rate, without any consequence for the black hole.     

Short-Time Nonlinear Effects in the Exciton-Polariton System

In the exciton-polariton system, a linear dispersive photon field is coupled to a nonlinear exciton field. Short-time analysis of the lossless system shows that, when the photon field is excited, the time required for that field to exhibit nonlinear effects is longer than the time required for the nonlinear Schrödinger equation, in which the photon field itself is nonlinear. When the initial condition is scaled by \(\epsilon ^\alpha \), it is found that the relative error committed by omitting the nonlinear term in the exciton-polariton system remains within \(\epsilon \) for all times up to \(t=C\epsilon ^\beta \), where \(\beta =(1-\alpha (p-1))/(p+2)\). This is in contrast to \(\beta =1-\alpha (p-1)\) for the nonlinear Schrödinger equation. The result is proved for solutions in \(H^s(\mathbb {R}^n)\) for \(s>n/2\). Numerical computations indicate that the results are sharp and also hold in \(L^2(\mathbb {R}^n)\).